1,3-benzodioxol-2-thiones,process of manufacture and method of use

ABSTRACT

1,3-BENZODIOXOL-2-THIONES OF THE FORMULA   2-(S=),4-R4,5-R3,6-R2,7-R1-1,3-BENZODIOXOLE   THEIR MANUFACTURE, THEIR UTILITY AGAINST PARASITIC NEMATODES PHYTOPATHOGENIC FUNGI AND REPRESENTATIVE OF THE ORDER ACARINA AND BIOCIDAL PREPARATIONS CONTAINING THEM ARE DISCLOSED. IN THIS FORMULA, R1 AND R2 EACH IS HYDROGEN OR HALOGEN; R3 IS HYDROGEN, HALOGEN, ISO-THIOCYANATE, LOWER ALKYL OR THE RADICAL-COR, WHEREIN R STANDS FOR LOWER ALKYL, LOWER HALOGENALKYL, LOWER ALKOXY, PHENOXY OR ANILINO; AND R4 IS HYDROGEN, HALOGEN OR LOWER ALKOXY; THE PROVISO IS THAT AT LEAST ONE OF R1 TO R4 IS DIFFERENT FROM HYDROGEN.

United States Patent 3,790,601 1,3-BENZODIOXOL-2-THIONES, PROCESS OF MANUFACTURE AND METHOD OF USE Jean-Jacques Gallay, Magden, Switzerland, assignor to Ciba-Geigy Corporation, Ardsley, N.Y.

No Drawing. Filed Jan. 26, 1971, Ser. No. 109,976 Claims priority, application Switzerland, Jan. 30, 1970, 1,387/70 Int. Cl. C07d 13/10 U.S. Cl. 260-3405 8 Claims ABSTRACT OF THE DISCLOSURE 1,3-benzodioxol-2-thiones of the formula their manufacture, their utility against parasitic nematodes phytopathogenic fungi and representatives of the order Acarina and biocidal preparations containing them are disclosed. In this formula, R and R each is hydrogen or halogen; R is hydrogen, halogen, iso-thiocyanate, lower alkyl or the radical-COR, wherein R stands for lower alkyl, lower halogenalkyl, lower alkoxy, phenoxy or anilino; and R4 is hydrogen, halogen or lower alkoxy; the proviso is that at least one of R to R is different from hydrogen.

The present invention concerns new 1,3-benzodioxazole-Z-thiones, processes for their production, their use in combatting parasitic nematodes, phytopathogenic fungi and members of the order Acarina as well as compositions containing the compounds as active ingredients.

The new 1,3-benzodioxole-2-thiones correspond to the Formula I wherein R and [R independently of each other represent hydrogen or halogen,

R represents hydrogen, halogen, isothiocyano, lower alkyl or the group COR wherein R represents lower alkyl, lower halogeno alkyl, lower alkoxy, phenoxy or anilino, and

R, represents hydrogen, halogen or lower al-koxy, whereby at least one of the symbols R to R, has a meaning other than hydrogen.

ice

The new 1,3-benzodioxole-2-thiones of Formula I are produced according to the invention by reacting a substituted pyrocatechol of the Formula II R4 wherein R R R and R have the meanings given under Formula I either with thio-phosgene in the presence of a base or with an N,N-disubstituted thiocarbamic acid halide.

For the reaction with thiophosgene, inorganic bases in particular are used, preferably alkali metal hydroxides. However, tertiary amines such as trialkylamines, pyridine and pyridine bases can also be used in the reaction. N,N- dialkyl thiocarbamic acid halides are the preferred N,N- disubstituted thiocarbamic acid halides, as well as N-halogeno thiocarbamyl derivatives of partially or completely hydrated nitrogen-heterocycles. It is advisable to conduct the reactions in solvents or diluents which are inert to the reaction components, e.g. in halogeno hydrocarbons such as chloroform, tri-chloro ethylene, carbon tetrachloride, etc. or hydro-carbons such as benzene, toluene, xylene etc.

The pyrocatechol derivatives of Formula II which serve as starting materials for the process according to the invention are known compounds or can be produced according to known processes.

The 1,3-benzodioxole-2-thiones of the Formula I have not yet been described. Halogenated benz-dioxolones are known from American patent specification No. 3,152,146, and halogenated 1,3-benz-oxathiol-2-ones are known from German patent specification No. 1,114,507. The compounds possess microbiocidal properties and are used as skin disinfectants. 1,3-benzoxathiol-2-oue (J. Chem. Soc. 1953 1514 et sec.), benzdioxolone (East German Pat. No. 57856) and 1,3-benzodioxole-2-thione [Ben 58 2154, (1925)] are known compounds.

The 1,3-benzodioxole-2-thiones of Formula I according to the invention possess valuable acaricidal and anthelmintic properties as well as activity against phytopathogenic fungi. The new active ingredients are nontoxic for both warm-blooded animals and plants whereby 1,3-benzothioxole-2-thiones of the Formula III:

the Formula IV wherein R represents hydrogen, chlorine or bromine and R represents bromine, methyl or chloracetyl.

The new active ingredients are particularly suitable for combatting parasitic nematodes, e.g. ascarides, trichostrongylides, strongylides, ancylostomatides and cestodes, e.g. taeniides, anoplocephalides, on domestic and farm animals such as cattle, sheep, goats, horses, pigs, cats, dogs and poultry. They can be dispensed to the animals in one shot dose as well as repeatedly, whereby the one shot doses according to the type of animal amount preferably to between 25 and 1,000 mg. per kgJbody weight. By a protracted closing a better effect is produced in some cases, or smaller total doses will suflice. The active ingredients or the mixtures containing them can also be added to the feed or to the drinks. The complete feed contains the substances of the Formula I, preferably in a concentration of about ODS-1% by weight.

The new active ingredients can be dispensed in the form of solutions, emulsions, suspensions (drenches), powders, tablets, boluses or capsule per-s or abomasal- 1y. Useful in the preparation of the above-identified application forms are, for example, the usual solid carriers such as kaolin, talc, bentonite, common salt, calcium phosphate, carbohydrates, cellulose powder, cottonseed meal, carbo-waxes, gelatine or liquids such as water, optimally with the addition of surface-active materials such as ionic or non-ionic dispersants as well as oils and other solvents and diluents not harmful to animal organisms. When the anthelminthic agents are present in the form of feed concentrates, useful carriers are, for example, production feeds, fodder grains or protein concentrates. Such food concentrates can also contain, apart from the active ingredients, additives, vitamins, antibiotics, chemotherapeutics, bacteriostats, fungistats, coccidiostats, hormone preparations, materials having anabolic action, or others favoring growth which influence the quality of the meat of slaughtered animals, or in other ways are useful for the organisms.

The new 1,3-benzodioxole-2-thionesof Formula I are also characterized by their fungicidal activity against numerous phytopathogenic fungi. These fungi causing plant disesases, for example powdery mildews such as cucumber powdery mildew (Erysiphe cichoraccarum), apple powdery mildew (Podosphaera leucotricha), rose powdery mildew (Sphacrotheca pannosa), wheat powdery mildew (Erysiphe gram-inis) as well as downy mildew such as those causing foliageand tuber-blight of potatoes (Phytophth o-ra infesians), the downygrape mildew (Plasmopora viticola), moreover leaf spot pathogens such as the pathogen causing tomato blight (Alternarz'a solani), the leaf spot disease of celery (Sepzoria wpicola) and rust fungi such as bean rust (Uromyces appendicitlatus), moreover the highly resistant common grey mold (Bon'yris cinera) etc., are killed by application of the new active ingredients or hindered in their growth. The compounds possess, as well as an excellent lasting effect. a good curative action whereby fungi which have already penetrated into the plant body are killed after application of the new compounds.

The new 1,3-benzodioxole-2-thiones of the Formula I show further good acaricidal properties and are best suited for combatting members of the order Acarina, especially normally-sensitive and resistant mites. By means of the new compounds, the mobile stages larva, Photonymphs, Deutonymphs and adults and the inactive stages (Nymphochrysalids, Deutochysalids and Teleochrysalids) as well as the eggs are killed within a few days. The new 1,3- benzodioxole-Z-thiones are, for example, suitable for combatting mites which belong to the following families: Tassonemidae e.g. Tassonumus/fragorzae, Tetranychidae, e.g. Tetranychus urticae, Tetranychus/relarz'us, Panonychus ulmi, Eriophyidae, e.g. Eriophyes ribis, Aceria sheldonis, and Phyllocopfurpa oleivorus.

The production of such pesticidal agents for plant protection according to the invention takes place according to a method known per se by intimate mixing and milling of the ingredients of general Formula I with suitable carriers, optionally with the addition of dispersants or solvents inert to theactive ingredients. The active ingredients can be used for the production of dusts, scattering agents, granulates, coated granulates, impregnated granulates, homogenous granulates, wettable powders, pastes, emulsions, solutions or aerosols.

For the production of solid preparations (dusts, powders, scattering agents or granulates) the active ingredients are mixed with solid carriers. Suitable particle size of the carrier in the case of dusts is up to about 0.1 mm., for scattering agents about 0.075 to 0.2 mm. and for granulates 0.2 mm. or more. Active ingredient concentrations in the solid preparations generally amount to 0.5 to To these mixtures there can be added moreover, stabilizers for the active ingredients and/ or nonionic, anionic active and cationic active materials which, for example, improve the adhesion of the active ingredient to the plant or plant components (adhesives and glues) and/or guarantee a better wettability (wetting agents) as well as dispersibility (dispersants) Active ingredient concentrates dispersible in water, wettable powders, pastes and emulsion concentrates are agents which can be diluted with water to any desired concentration. They consist of active ingredient, carrier, optionally additives which stabilize the active ingredient, surface active substances and anti-foam agents, and optionally solvents. The active ingredient concentration in these agents amounts to in general 0.1 to 95%, especially 5 to 80%. When the application is made from an aeroplane or other suitable application apparatus, preparations containing up to 99.5% of active substance or even pure active substance are used. The wettable powders and pastes are obtained by mixing and milling to homogeneity the active ingredients with dispersants and pulverized carriers in a suitable apparatus. In many cases it is advantageous to use mixtures of different carriers. As anti-foam agent, silicones may for example be mentioned. The active ingredients are mixed, milled, sieved and sifted with the above mentioned additives in such a way that the solid component does not exceed a particle size of 0.02 to 0.04 mm. in the case of wettable powders and in the case of pastes does not exceed 0.003 mm. For the production of emulsion concentrates and pastes dispersants, organic solvents and water are used. The solvent must be practically odorless, not phytotoxic, inert to the active ingredients and must not be easily combustible.

Moreover, the agents according to the invention can be used in the form of solutions. T 0 this end the active ingredient or ingredients of Formula I are dissolved in a suitable organic solvent, solvent mixtures or water. The solutions should contain the active ingredients in a concentration within the range of from 120%. Other biocidally active ingredients or agents can be admixed with the agents described according to the invention. Thus, the new agents can contain, apart from the compounds of the Formula I, other fungicides, for example insecticides, herbicides, bacteriocides, fungistats, bacteriostats or nematocides for the extension of the active spectrum. The agent according to the invention can moreover contain also plant fertilizers, trace elements etc.

The following examples further describe the production of the compounds of the invention and compositions containing them as well as their application, but in no way limit the scope of the invention. The temperatures are given in degrees centigrade.

EXAMPLE 1 830 ml. of 10% aqueous sodium hydroxide solution are added dropwise with stirring at 10-15 during 50 minutes to a solution of 186.6 g. of 4-chloracetyl pyrocatechol and ml. (138 g.) of thiophosgene in 1250 ml. of chloroform. The reaction mixture is stirred for 3 hours at room temperature and the solvent distilled off in vacuo at 40. The suspension remaining is diluted with water, the solid separated off and dried. The S-chloroacetyl-1,3-beuzodioxole-2-thione, recrystallized from benzene/petrol ether, has melting point 135-138". (Compound No. 1.)

EXAMPLE 2 830 ml. sodium hydroxide solution are added dropwise with stirring at 1 0-15 during 50 minutes to a solution of 268 g. of 4,5-dibromo pyrocatechol (M. Kohn Am. Soc., 73, 480 (1951); M.P.: 121) and 85 ml. (128 g.) thiophosgene in 900 ml. of chloroform. After stirring for 3 hours at room temperature the solvent is distilled off at 40 in vacuo and the suspension remaining is diluted with 500 ml. of water. The crystalline solid is separated ofi, dried and recrystallized from benzene/ cyclohexane. The 5,6-dibromo-1,3-benzodioxole-2-thi0ne has melting point 159-161. (Compound No. 2.)

The following 1,3-benzodioxole-2-thiones were obtained analogously to the foregoing examples.

M.P. No. Compound ln C.

3--- fi-chloro-l,3-benzodioxole-2-thione. 94-101 4 d-ohloro-l,3-benzodioxole-2-thlone. 105-107 5 5-bromo-1,3-benzodioxole-2-thione 132-135 6-. 4,6dichloro-1,3-benzodioxole-2-thione- 72-73 7 5,6-dichloro-l,3-benzodioxole-2-thione 154-156 5 bromo-6-chloro-1,3-benzodioxole-2-thlone 140-143 4,5,6-trichloro-1,3-benzodloxole-2-thione 127-130 4,5,6-tribromo-1,3-benzodioxole-2-thione 163-166 4,5,6,7-tetrachloro-1,B-benzodioxole-Z-thione- 210-213 4,5,6,7-tetrabromo-1,3-benzodioxole-2-thione 308-310 5-methyl1,3-benzodioxole-2-thione 116-117 Gethyl-l,3-benzodioxole-2-thione 73-76 6-chloro5-methyl-1,3-b enzod1oxole-2-thione 155-156 16 5-bromo-6-methyl-1,3-benzodioxole-Z-thlone. 165 17- 5-lsotl1iocyano-1,3-benzodioxole-2-thione 125-126 18. 4-methoxy-1,3-benzodioxole-2-thione 140-142 19. fi-acetyl-l,3-benzodioxole-2-thione-. 153-155 20- 5-propionoyl-1,3-benzodioxole-2-thion 107-110 21- 5-methoxycarbonyl-1,3-benzodioxole-2-thlone.. 113-115 22 G-ethoxycarbonyl-l,3-benzodioxole-2-thione 93-94 23.. fi-phenoxycarbonyl-1,3-benzodioxole-2-thione. 110-113 24.. fi-(N-phenylcarbamyl)-1,3-benzodioxole-2-thion 214-217 25- 5-chloracetyl-6-bromo-benzodioxole-Z-thione. 125-128 26.. fi-ethyl-6-bromo-benzodioxole-Z-thione 113 27 5-chloracetyl-6-methyl-benzodioxole-2-thione 136 28.- 5-chloracetyl-6-chloro-benzodioxole-2-thione. 29.. 5-n-butyl-1,3-benzodioxole-2-thione 5-bromoacetyl-1,3-benzodioxole-2-thione.- fi-dichlorocetyl-l,B-benzodioxole-Z-thlone-.

EXAMPLE 3 (All parts are given by weight) (I) Dusting powder (plant protection) For the production of (a) 10% and (b) 2% dusting powder, the following constituents were used:

10 parts of S-chloracetyl-1,3-benzodioxole-2-thione 5 parts highly dispersed silicic acid 85 parts talc 2 parts 5,6-dibromo-1,3-benzodioxole-2-thione 1 part highly dispersed silicic acid 97 parts tale The active ingredients given above were intimately mixed and milled with the carriers. The fungicidal dusting agent so obtained is useful for treating soil for seed beds or for dusting of plants.

obtained in powder form are suitable for the treatment of seeds of all types. 75

6 (III) Wettable powder (plant protection) For the production of (a) 10%, (b) 50% and (c) wettable powder, the following constituents were used:

50 parts 5,6-dibromo-1,3-benzodioxole-2-thione 5 parts naphthalene sulphonic acid-phenol sulphonic acidformaldehyde condensate (3:2:1) 1 part dibutyl naphthalene sulphonic acid-sodium salt 2 parts 1 :1 mixture of hydroxy ethyl cellulose and French chalk 20 parts sodium aluminum silicate 22 parts kaolin 80 parts S-chloroacetyl-l,3-benzodioxole-2-thione 5 parts formaldehyde-naphthalene sulphonic acid sodium salt condensate 2 parts saturated fatty alcohol sulphates 2 parts 1:1 mixture hydroxy ethyl cellulose and French chalk 11 parts sodium aluminum silicate The active ingredients are mixed with the carriers and dispersing agents and finely milled. A wettable powder is obtained with excellent wettability and suspension properties. Suspensions of any desired concentration can be obtained from such wettable powders by adding water. They can be used for the treatment of cultivated plants such as stone fruit trees or pomaceous fruit trees, ornamental shrubs and ornamental plants of all types, vegetables, etc.

(IV) Dispersible powders (as feed additives) For the production of a 50% dispersible powder there were used:

50 parts S-methoxy-1,3-benzodioxole-2-thione 1 part polyethyleneoxypropylene glycol with a molecular weight of about 2000 (Pluronic L 61) 5 parts ammonium salt of a sulphonated naphthalene sulphom'c acid-phenol-formaldehyde condensate (Irgatan A61) 44 parts kaolin 50 parts 5,6-dichloro-1,3-benzodioxole-2-thione 1 part polyethylenoxypropylene glycol with a molecular weight of about 8000 (Pluronic F 68) 0.5 part sodium lignin sulphonate 48.5 parts sodium silicate The said active ingredients were mixed with the carriers and dispersion agents and finely milled. The powder obtained can be mixed with liquid or pulpy feeds and administered to domestic or farm animals.

(V) Pastes (plant protection) For the production of a 25% paste the following materials were used:

25 parts S-chloroacetyl-1,3-benzodioxole-2-thione 10 parts lignin sulphonic acid (50% aqueous solution) 10 parts ethylene glycol 55 parts water The active ingredient and the dispersing agent were intimately mixed. A paste is obtained which can be diluted with water to suspensions of any desired concentration. Such suspensions are suitable for the treatment of cultivated plants such as, for example, roses, fruit 8 lar weight of about 3000 (Pluronic L 64) 96 parts glycol monoethyl ether an emulsifiable concentrate is obtained which can be diluted with water to emulsions of any desired concentrees and vegetables. tration and which can be administered, for example, as

a drink to domestic and farm animals. (VI) Paste (feed stuif) For the production of a 40% paste the following ma- EXAMPLE 4 terials were used: 40 parts S-chloracetyl-1,3-benzodioxole-2-thione (I) i sfi fig zg gz g are Infested 2.5 parts sodium lignin sulphonate g 0.3 art sodium benzoate 10 g glycerine 1- to 3-day old chicks were infested artificially with 47 2 parts distilled water eggs of the Ascaridia galli. Groups of 5 chickens were used in each experiment. 4 to 5 weeks after infestation The ac V6 mgl'edlellt and the f P Qgellt Q the active ingredients were administered to the birds in 1llt1mat61Y- The Paste 9btal1 1ed 1S admlxefl with one dose per day on 3 consecutive days. As controls there llquld P PY feeds for admmlstratlon to domestlc and were used infested hens which were not medicated. farm ammals.

(VII) Emulsion concentrate (plant production) Evaluation gg 5533 55 231 zig ggg The number of Ascaridia galli eliminated per experig mental group during the course of 5 days after the first 10 parts 5,6-dibromo-1,3-benzodioxole-2-tb1one administration of the active substance were determined parts dimethyl formamide daily and the number still detectable in the intestine on 50 parts petrol (boiling range 230-270 C.) dissection on the fifth day of the experiment was like TABLE 1 Ascan'dia galli Ascuridic qalli Daily dose in Par experi- Per test No. of mg./kg. ment day bir wormbody and group iound on tree Active ingredient eliminated dissection hens 4-methoxy-1,3-benzodioxole-2- 500 142 20 4 5-is0thiocyano-l,3-benzodioxole-2- hinnn 500 216 0 5 5-bromo-1,3-benzodioxoie-2-thione- 500 94 0 5 5-bromo-6-ch1or0-l,3-benzodioxoie-2-thinnn 750 38 2 4 5-methy1-6-chlor0-l,B-benzodioxole-2- 750 60 0 5 1,3-henzodioxole-2-thlone known from Ber. 58, 2,154 (1925)..- 200 47 101 5,6-diehloro-l,3-benzodloxole-2-one known from U.S.P. No. 3,152,146..-- 750 2 143 0 l 3 dead birds.

5 parts of a combined emulsifier consisting of the Ca salt wise counted. Moreover, the number of worm-free hens of dodecyl benzene sulphonic acid and the condensawas determined. E Product 3 ethylene oxlde i i ml Anthelmintic action on mice attacked by Emullat WK --manufacturer Umon Ch1m1que Belge Hymenolepszs name S.A., (Brussells). Th d dm eactive in e ien er i The active ingredient concerned is dissolved in petrol of a Sus e s 0 w g g m e fol-m or dimethyl formamide and this solution is then added p nsi r S omac 6 o w mice to the combined cmulsifier Emulsion concentrates are which were infested with Hymenolepszs mma. For each obtahed hi h an b dil with water to emulsions of experiment 5 animals were used. The active ingredients n c m Such em lsions are suitable were administered to each animal once a day for three 3 g z 'such as for consecutive days. On the 8th day after the beginning of 5 t nd 6 gable the treatment the animals were killed and dissected. am? roses tees a v g The evaluation took place after dissection of the ex- (VIII) E ul ifi bl concentrat (drinks) perimentai animals by counting the tape worms found B mixing in the intestine. As controls there were used untreated,

y simultaneously infested mice of the same type. 2 parts 5,6-dibromo-1,3-benzodroxole-2-thione The agents were tolerated by the mice without any 2 parts polyethyleneoxypropylene glycol with a molecusymptoms.

TABLE 2 Hymcnolepaia mm:

Infestation oi the Infestation oi Pally dose 5 experimental the control in mgJkg. animals on animals on Active ingredient body weight dissection dissection 4-methoxy4,3-benzodioxole-2 500 0-00-00 9 5,6-dichloro-1,3-benzo "2- 500 0-0-0-0-0 9-4-3-5-4 5-chloraeety1-1,3-benzodioxole-2-thione- 500 0-0-0-0-0 9-4-3-5-4 4,5,fi-tribomo-1,3-beuzodioxole-2- 750 0-0-0-0-0 7-9-8-11-12 5brom0-1,8-benzodioxole-2-thione 300 0-0-0-0-0 11-8-7-8-13 4,6-dich1oro-1,3-benzodioxol 750 0-0-0-0-0 3-3-1-3-1 4,5,6-triehloro-l,3-benzodioxole-2- 1,000 0-0-0-0-0 11-878-13 5-isothiocyano-1,3-benzodioxole-2- 750 0-0-0-0-0 1-7-5-5-6-9 5-ethyl-l,3-benzodioxole-2-thione. 750 0-0-0-0-0 0-1-1-2-3 5,6-dichloro-l,3-benzodioxole-2one known from U.S.P. No. 3,152,146 750 3-2-6-1/1 dead 11-16-12-20-10 1,3benzodioxole-2-one; known from German Patent No. 57856 Beilst. 19.1 15-11-2-7-4 4-80-35-9-0 5-bromo-6-ch1oro-1,3-benzodioxoie-2-thi0ne 750 0-0-0-0-0 0-1-1-2-3 fi-methyl-fi-chloro-l,3-benzodioxole-2- 750 (HHHH) 0-1-1-2-3 5-chloracetyl-6-methy1-l,3-benzodi0xole-2-thi0ne 750 (HHHH) 1-12-3-3 (III) Anthelminthic action on mice attacked by mouse Oxyuris The active ingredients were administered in the form of a suspension by a stomach probe to white mice which 10 In the following table: 10=inactive, attack of strength as untreated control plants 9-1=reduction of attack according to linear assessment 5 O=no attack were infested with mouse Oxyuris. The active ingredients E he cbhomce m were administered to each animal once daily over three ry l a m consecutive days. The animals were then killed on the Table 5 8th day after the beginning of the treatment and dissected. 4-methoxy-1,3-benzodioxole-2-thione 5 The evaluation took place after dissection of the experi- 10 S-chloracetyl-1,3-benzodioxole-2-thione 3 mental animals by counting the mouse Oxyuris found in 5,6-dibromo-1,3-benzodioxole-2-thione 5 the intestine. As controls there were used untreated, in- 4,5,6,7-tetrachloro-1,3-benzodioxole-2-thione fected mice of the same type. S-(N phenylcarbamyD-1,3-benzodioxole-2-thione 3 The agent was tolerated by the mice without trace of 1,3-benzodioxole-2-thione known from Ber. 58, 2154 any symptoms. (1925 10 TABLE 3 Mouse Ozyuria Daily dose Infestation of the Attack of in mg./kg. experimental the control body animals on animals on Active ingredient weight dissection dissection 5,6-dich1oro-l,3-benzodioxole-2-thinne 500 0-0-0-0-0 3-51-58-9-4 4-methoxy-l,3-benzodiox0le-2-thinne 500 0-0-0-0-0 1-9-8-50-23 5,6-dibromo-l,3-benzodioxole-Z- 500 0-0-0-0-5 12-5-18-0-12 5-bromo-1,3-benzodiozole-2-thione 300 00-000 3-11-2-6-4 4,6-dich1oro-l,3-benzodioxole-2- 750 0-0-0-0-2 42425611 4,5,6-trichlo1o-1,3-benzodioxole-2 one 1, 000 0-0-0-0-0 47121024 4,5,6,7-tetrachloro-1,3-benzedioxole-2- 750 0000-0 3-11-2-6-4 5-isothiocyano-1,3-benzodioxole-2-thiene 750 O-O-O-O-O 3-2-2-3-2 5-propionoyl-1,3-benzodioxol-2-thinne 750 000-00 14-21-8-14-9 5-(N-phenylcarbamyl)-1,3-benZodi0x0le-2-thione 750 0000-2 -12-8-13-11 5-bromo-6-chloro-1,3-benzodioxole 2- 750 00-000 5-8-10-13-32 5,6-dibromo-1,B-benzodioxole-Z-one known from U.S. Patent No. 3,152,146 750 4-7-2-8-4 4-7-12-10-24 5,6-dichloro-l,3-benzodioxole-2-one known from U.S. Patent No. 3,152,146. 750 299210 1 dead 14-21-8-14-9 1,3-benzoxathiole-2-one known from J. Chem. Soc., 1953 1,514 at sec- 500 15-15-27-14-20 3-51-58-9-4 5-methyl-6-chloro-l,3-benzodioxo1e-2-thione 750 0-0-0-0-0 5-8-10-13-32 EXAMPLE 5 (I) Action against Botrytis on Vicz'a faba (soya beans) In Petri dishes which were provided with moistened filter paper there were placed 3 well-developed leaves each of the same size of Vicia faba which were sprayed until dripping wet with a brew (0.1% active substance content) of an active substance formulated as a wettable powder. When the leaves were again dry, they were infected with a freshly prepared spore suspension of the fungi. After the leaves had been maintained for 1 to 2 days in a moist atmosphere at 18 to 20 C. black specks, which first formed as points but quickly spread out, appeared on the leaves. The number and size of the infection points served as an evaluation scale for the effectivity of the test substance.

In the following table:

10=ineifective, attack of same strength as untreated control plants; 9-1 =reduction of attack according to linear estimation,

=no attack (11) Action of Erysiphe cichoracearum (cucumber mildew) on Cucumz's sativus (cucumber) Young cucumber plants were sprayed with a spore suspension of the cucumber mildew. After first spraying (dripping wet) with a 0.1% suspension of the active ingredient formulated as wettable powder and drying the spray coating, they were then placed in a greenhouse at 23 C. After 8 days the level of attack (proportion of the leaf surface covered with the fungal coating), on the infected treated leaves was ascertained in comparison with the untreated infected controls.

(III) Action on Uromyces appendiculates (bean rust) on beans (Phaseolus vulgaris) Bean plants at the 2-leaf stage were sprayed with a suspension of the substance formulated as wettable powder until dripping wet (concentration 0.1% of active substance). When the plants were again dry they were infected with a fresh spore of bean rust (5 plants per product) and then maintained for one day in a moist chamber, then in a greenhouse at 2022 C. Experimental evaluation was made according to the number of pustules present after about 8 to 12 days.

In the following table:

10=inactive, attack of same strength as untreated control plants, 91=reduction of attack according to linear assessment 0=no attack.

Urom-yces appendiculates Table 6 5,6-clichloro-1,3-benzodioxole-2-thione 3 5,6-dibromo-1,3-benzodioxole-2-thione 5 4,5,6,7-tetrachloro-1,3-benzodioxole-2-thione 3 1,3-benzodioxole-2-thione known from Ber. 58, 2154 Activity on phytopathogenic fungi in open land Celery with leaf spot disease (Septaria apicola). Cucumber with powdery mildew (Erysiphe polyphaga).

11 Sugar beets with leaf spot disease (Cercospom belicola).

Tomatoes with leaf spot disease (Alternaria solani).

12 What is claimed is: 1. 1,3-benzodioxol-2-thione of the formula B To do this the corresponding parcels were covered with l l a plastic tent. The plants were infected with the spore 5 R suspension and then sprayed over 48-72 hours with water in a cloud-like distribution. .o

The treatments were carried out with 0.1% dispersions of active ingredient (obtained from 50% wettable powders) with a knapsack sprayer (2.5 atm.). wherein For the naturally infected grapes and wheat, the treatments followed after intervals of 1 to 2 weeks. 8 to 10 1 and 2 each is a member selected from the group treatments were carried out during the main vegetation @nsisting 0f hydrogm and halogen; time; readings were taken everyzweeks R3 a. member SelCCtEd from the group consisting Qf Cucumber, celery, sugar beets and tomatoes were each 1 y f halogen, iso-thiocyanate, lower alkyl and the treated at intervals f about one week as follows; radical COR, R being a member selected from the group consisting of lower alkyl, halogen lower alkyl, TREATMENTS lower alkoxy, phenoxy and anilino; and

Gucum- Sugar Toma R is a member selected from the group consisting of bets Celery beats me hydrogen, halogen and lower alkoxy with the proviso Before infection 2 2 2 1 that at least one of R to R is different from hydrogen. 2% iiihigi iiiaanas'airzeta; 4 12 7 x 2. 1,3-benzodioxol-2-thione according to claim 1 of the (X/Y), days 3 1 5 2-3 4/1-2 3/10 formula R'1 The evaluation was made according to the following 0 index: I

0 no fungal growth R: o =intermediary stages of fungal growth R;

wherein 3=funga1 gmwth=cnu1 R' R and R' each is a member selected from the group The values given in the following table table represent Consisting of hydrogen and halogen and the average of the single readings made by visual evalua- 's is a member Selected fI'Om the group consisting of 1 halogen, halogen lower alkanoyl and lower alkyl.

AS comparative products the following commercial 3. 1,3-benzodioxol-2-thione according to claim. 2 0f thB products were used in this experiment: formula (1) Triphenylzinc hydroxide. o 2 7-methy1 '1,3-dithiolo[4,5-b]quinoxaline 2 one 40 T [Morestan]. I (3) 1,4-dithia-anthraquinone 2,3 dicarbonitrile[D'e- 0 These products applied in the same concentration Wherem showed an insufficient effect (3) against downy and pow- R" is a member selected from the group consisting of dery mildew and also against leaf spot disease or were hydrogen, chlorine and bromine and R" is a member proved to be phytotoxic especially in the case of triphenylselected from the group consisting of bromine, methyl zinc hydroxide. and chloroacetyl.

TABLE 1 Plasma- Erysiphe Cerospora as: asta: ars: as: are Active ingredient (grapes) (wheat) bar) (c eilery) be et) (tomato) Behloracatyl-l,3-benzodioxide-2-thione..- 0 1 0 5,6-dibromo-1,3-benzodioxide-2-thione 1 0 1 1 0 EXAMPLE 6 4. The compound according to claim 3 of the formula Acaricidal activity /0 For the determination of acaricidal activity bean leaves BF 1 were used which were infested by adults, inactive stages and eggs of the red spider mite (Tetranychus urticae). Br O The leaves were treated with 0.1-, 0.05- and 0.01% aqueous emulsions of the substance to be tested (prepared e Compound according to Claim 3 of the formula from a 10% emulsifiable concentrate). The concentration of active substance was determined which produced 100% C1 s mortality after 6 days. The animals used in the experiment were red spider mites of a strain resistant to phosphoric acid esters.

100% morta ty within 5 days The compound according to claim 3 of the formula with an active substance concentration of x percent for 0 Cl 8 Inactive Active substance Adults stages Eggs C T 5,6-dibromo-l,3-beuzodioxoIe-2-thione. 0. 01

7. The compound according to claim 3 of the formula that at least one of R to R is difierent from hydrogen which comprises reacting a pyrocatechol of the formula OTS R! R -OH CICHzC 5 7 8. Process for the manufacture of 1,3-benzodioxo1-2- R 4 throne of the formula 10 wherein R to R have the meaning set forth above with (a) thiophosgen in the presence of a basic compound or (b) a N,N-dialkylthiocarbamic acid halide.

R 0 8 References Cited 1 UNITED STATES PATENTS R a I 3,378,592 4/1968 Lutz zso s4o.sx

FOREIGN PATENTS Thomae, Chemical Abstracts, vol. 54 (1960), col. R and R each is a embe l cted from th rou consistin g of hydrog h and hi lcfgen; e g p Adley et al., Chemical Abstracts, vol. 67 (1967), col. R is a member selected from the group consisting of 5 10954111" hydrogen, halogen, iso-thiocyanate, lower alkyl and the 2 radical --COR, R being a member selected from the ALEX MAZEL Pnmary Exammer group consisting of lower alkyl, halogen lower alkyl, J. H. TURNIPSEED, Assistant Examiner lower alkoxy, phenoxy and anilino; and R is a member selected from the group consisting of US. Cl. X.R.

hydrogen, halogen and lower alkoxy with the proviso 30 424-482 wherein 

